Shelf stable haze free liquids of overbased alkaline earth metal salts, processes and stabilizing halogen-containing polymers therewith

ABSTRACT

Shelf stable haze free liquids of overbased alkaline earth metal salts are obtained by reacting metal base with fatty acids in the presence of liquid hydrocarbon and aliphatic alcohols having at least 8 carbon atoms to provide overbased liquids essentially free of a phenol or a phenolic derivative. Stabilizer compositions containing the overbased liquids and mixed metal stabilizers of zinc, cadmium and tin are provided for stabilizing halogen-containing polymers.

FIELD OF THE INVENTION

[0001] The present invention relates to a shelf stable haze free liquidof an alkaline earth metal salt of a fatty acid and a process ofproducing the liquids. Mixed metal stabilizers containing the overbasedliquids and metal carboxylates of zinc, cadmium or alkyltin are providedand used as stabilizers for halogen-containing polymers such aspolyvinyl chloride (PVC).

BACKGROUND OF THE INVENTION

[0002] The preparation of overbased calcium or barium salts ofcarboxylic acids, alkyl phenols, and sulfonic acids are disclosed in thefollowing U.S. Pat. Nos.: 2,616,904; 2,760,970; 2,767,164; 2,798,852;2,802,816; 3,027,325; 3,031,284; 3,342,733; 3,533,975; 3,773,664; and3,779,922. The use of these overbased metal salts in thehalogen-containing organic polymer is described in the following U.S.Pat. Nos.: 4,159,973; 4,252,698; and 3,194,823. The use of overbasedbarium salt in stabilizer formulations has increased during recentyears. This is due, in the main, to the fact that overbased barium saltspossess performance advantages over the neutral barium salts. Theperformance advantages associated with overbased barium salts are lowplate-out, excellent color hold, good long-term heat stabilityperformance, good compatibility with the stabilizer components, etc.Unfortunately, most of the overbased barium salts are dark in color and,while these dark colored overbased barium salts are effectivestabilizers for halogen-containing organic polymer, their dark colorresults in the discoloration of the end product. This featureessentially prohibits the use of dark colored overbased barium salts inapplications where a light colored polymer product is desired.

[0003] According to the teachings of U.S. Pat. No. 4,665,117, lightcolored alkali or alkaline earth metal salts are prepared where alkylphenol is used as a promoter. However, alkyl phenol is also a majorcause for the development of color in the final product. This problem isovercome by the use of propylene oxide which displaces the hydrogen ofthe phenolic hydroxyl group and thereby restricts the formation ofcolored species. However, there are disadvantages associated with thisapproach, principally due to the toxic nature of propylene oxide.Propylene oxide is classified as a possible carcinogen and laboratoryanimal inhalation studies have shown evidence of a link to cancer.Propylene oxide is also listed as a severe eye irritant, and prolongedexposure to propylene oxide vapors may result in permanent damage to theeye. Furthermore, propylene oxide is extremely flammable and explosivein nature under certain conditions. Propylene oxide boils at 94° F. andflashes at −20° F. As a result, extreme precautions are required tohandle propylene oxide at the plant site. Special storage equipment isrequired for propylene oxide and other safety features are necessary.U.S. Pat. No. 4,665,117 describes the use of propylene oxide at 150° C.At this temperature, propylene oxide will be in the gaseous phase. Underthese operating conditions, more than stoichiometric amounts ofpropylene oxide are required to carry the reaction to completion becausepropylene oxide will escape from the reaction mixture and this requiresadditional handling of the excess propylene oxide.

[0004] With the movement in the plastics industry to remove heavymetals, liquid calcium-zinc stabilizers are desirous, but not practical,as replacements for barium-cadmium or barium-zinc. Low metalconcentrations, poor compatibility, haziness in clear products and plateout during processing in PVC have severely limited the universalacceptance of calcium based liquid stabilizer compositions. Problems areencountered in the stability of these compositions upon standing orstorage. Storage stability is due to the incompatibility among the metalsalts employed in the composition and is exhibited by increasedturbidity, viscosity, or insoluble solids over time. As a result, theliquid calcium compositions are no longer homogeneous or readilypourable and must be specially treated in order to be used. U.S. Pat.No. 5,322,872 is directed to stabilized compositions of mixed metalcarboxylates having improved storage stability. According to thispatent, a complexing agent is added to the mixed metal carboxylate inorder to improve shelf stability. Complexing agents disclosed in thispatent include phosphines, phosphites, aromatic cyanides, aromatichydroxy compounds, oximes and other compounds. U.S. Pat. Nos. 5,830,935and 5,859,267 have also issued as directed to processes for improvingbasic metal salts and stabilizing halogen-containing polymers therewith.

[0005] Notwithstanding the state of the art as exemplified by the abovepatents, there is a need for further improvements in making shelf stablecompositions of overbased alkaline earth metal carboxylates and inmethods for their use in stabilizing halogen-containing polymers.

SUMMARY

[0006] The present invention relates to a shelf stable haze free liquidof an overbased alkaline earth metal salt of a fatty acid. In apreferred form, these liquids contain an alkaline earth metal carbonate,an alkaline earth metal carboxylate of a fatty acid, a liquidhydrocarbon, and an aliphatic alcohol having at least 8 carbon atoms.These liquids are referred to sometimes hereinafter more simply as“overbased alkaline earth metal salt(s)” or “overbased alkaline earthmetal carboxylate(s)/carbonate(s)”. Liquid overbased calcium and bariumsalts are preferably provided and, in a preferred form of the invention,the liquids are essentially free of a phenol or a phenolic derivative.

[0007] The invention also relates to a process for preparing the shelfstable haze free liquid of an overbased alkaline earth metal salt of afatty acid. The process involves reacting an alkaline earth metal baseand a fatty acid with an equivalent ratio of metal base to fatty acidbeing greater than 1:1 in the presence of a liquid hydrocarbon. Asurfactant and catalyst are used to promote the reaction. The mixture isacidified, preferably by carbonation, to produce an amorphous alkalineearth metal carbonate. During carbonation, a dispersion of alkalineearth metal base, a liquid hydrocarbon, and an aliphatic alcohol havingat least 8 carbon atoms, is added in relative amounts to produce astable haze free liquid reaction product. Water is removed from thereaction product to obtain a shelf stable haze free liquid overbasedalkaline earth metal salt.

[0008] It has been found important during carbonation to add thedispersion of metal base, liquid hydrocarbon and aliphatic alcohol inrelative amounts at a controlled rate to produce the stable haze freereaction product. There are a number of reasons which are believed tocontribute to the formation of a stable haze free liquid which is thenfilterable to remove impurities and byproducts of the reaction. Up tothe discoveries made in accordance with the principles of thisinvention, it was not considered possible to make in a practical orcommercial operation an overbased calcium fatty acid salt, for example,that may be filtered at commercial or practical rates to remove unwantedimpurities and byproducts of the reaction to produce a shelf stable hazefree liquid. In contrast, it has been found that by the continuousaddition of the dispersion or slurry of base during carbonation, suchresults are achievable. It is believed that the metal base slurryprevents the formation of undesirable calcium carbonate crystals orbyproducts in the desired overbased metal salt. These undesirablemoieties prevent the formation of stable haze free products which arefilterable. In other words, the metal base slurry is added at acontrolled rate which does not exceed the rate of the desiredproduct-forming reaction. The reaction is controlled by continuous orincremental addition of the metal base to make the calcium ionsimmediately available for the desired reaction as opposed to allowingthe metal base, for example lime, to react and form a byproduct.Excessive byproduct or lime coated with calcium carbonate is believed torender the liquid product unfilterable. Using this procedure, the pH iscontrolled during the reaction so that the fatty acid is neutralized andthe pH rises to about 10-12 with the continued addition of base toproduce dissolved metal ion which reacts with CO₂ during carbonation toproduce the desired product. It is believed if the reaction rate is notcontrolled, and the base is not dissolved, then solid base reacts or iscoated with calcium carbonate to form undesirable byproducts. Theformation of undesirable byproducts of the reaction renders the finalproduct unstable and unfilterable.

[0009] The haze free liquids of the overbased alkaline earth metal fattyacid salts are suitable for use in making mixed metal stabilizercompositions with zinc, cadmium or alkyltin carboxylates. Other metalcompound stabilizers that are well known may be used where the metalcomponent can also be barium, calcium, strontium, lead, bismuth orantimony, and mixtures thereof. The mixed metal stabilizer compositionsprovide heat and/or light stability to vinyl halide resins such aspolyvinyl chloride (PVC), and the like.

[0010] A number of benefits are obtained by the products and processesof this invention. Improvements in shelf stability of liquid overbasedalkaline earth metal fatty acid salts are achieved. In particular, shelfstabilities are achieved with the liquids being free of phenol andphenolic derivatives such as phenolic reaction products. This is anespecially desirable advantage in view of the efforts of the trade toreduce or eliminate such phenolic products because of environmentalconcerns. Also, as developed above, such phenols are a source of colordevelopment. In addition, enhanced shelf stability for the liquidoverbased calcium fatty acid carboxylates and mixed metal stabilizercompositions of the invention have been demonstrated over presentlycommercially available products. In particular, presently availableliquid overbased calcium fatty acid carboxylates exhibit the developmentof turbidity or haze, whereas the liquid compositions of this inventionremain stable over extended periods of time. Therefore, the haze freeliquids of this invention allow easy handling, storage and filtration.Furthermore, when the mixed metal stabilizer systems containing liquidoverbased barium or calcium carboxylates are employed in vinyl halidepolymers, they exhibit better compatibilities with improvements inthermal stability, clarity and plate out resistance.

[0011] The above advantages, benefits and further understanding of thisinvention will be apparent with reference to the following detaileddescription and preferred embodiments.

DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS A. Shelf Stable Haze FreeLiquids of Overbased Alkaline Earth Metal Salts

[0012] In one preferred form of the invention, the shelf stable hazefree liquid of an overbased alkaline earth metal salt of a fatty acidcomprises

[0013] an alkaline earth metal carbonate,

[0014] an alkaline earth metal carboxylate of a fatty acid,

[0015] a liquid hydrocarbon, and

[0016] an aliphatic alcohol having at least 8 carbon atoms, with theliquid being preferably free of a phenol or a phenolic derivative suchas a phenolic reaction product.

[0017] In another form of the invention, the alkaline earth metalsulfate, sulfide or sulfite may be formed instead of the carbonate wherethe acidic gas used in the process is sulfur dioxide, sulfur trioxide,carbon disulfide, or hydrogen sulfide.

[0018] The fatty acid of the overbased liquid carboxylate is generally aC₁₂-C₂₂ fatty acid, including, for example, lauric, myristic, palmitic,stearic, archidic and behenic, among the saturated fatty acids.Unsaturated fatty acids include palmitoleic, oleic, linoleic, andlinolenic. Among these fatty acids, oleic is presently preferred inpreparing the overbased liquid carboxylates.

[0019] The alkaline earth metal of the salt is selected from the groupconsisting of calcium, barium, magnesium and strontium. For example,shelf stable haze free overbased calcium oleates have been prepared.These overbased calcium salts contain calcium carbonate, calcium oleate,a liquid hydrocarbon diluent and an aliphatic alcohol having at least 8carbon atoms.

[0020] In a broad form of the invention, it is important to have analiphatic alcohol having at least 8 carbon atoms, more preferably analcohol having 8 to 14 carbon atoms, such as, isodecanol, dodecanol,octanol, tridecanol and tetradecanol. Isodecanol is presently preferred.It has been found that when a higher aliphatic alcohol is employed inmaking the overbased product, phenol may be excluded from the reactionas a promoter. This is a particularly advantageous feature of theinvention where it is undesirable to have a phenol or phenolic reactionproduct involved in the manufacture or use of the overbased liquid.

[0021] In another form of the invention, the liquid overbased alkalineearth salt of the fatty acid is believed to be a thermodynamicallystable microemulsion. The microemulsion has micells and a continuousphase. The micells consist of an alkaline earth metal carbonate and analkaline earth metal carboxylate of the fatty acid. The continuous phaseof the microemulsion consists of the liquid hydrocarbon and the higheraliphatic alcohol.

[0022] Haze free liquids of the overbased metal salts have been preparedcontaining at least 4% by weight or more of the alkaline earth metal upto about 36% by weight. In the case of the overbased calcium salts, upto about 13-15% by weight calcium are produced and, for barium salts, upto about 36% by weight barium may be produced. In the preparation ofhigher overbased products, for example, containing about 13-15% byweight metal, it has been found suitable to use a glycol or a glycolether along with the higher aliphatic alcohol. A glycol or glycol ethermay be selected from the group consisting of diethylene glycol monobutylether (butyl Carbitol®), triethylene glycol, dipropylene glycol,diethylene glycol monomethyl ether, ethylene glycol monobutyl ether, andmixtures thereof.

B. The Basic Process and Critical Features

[0023] The process of the present invention for preparing a shelf stablehaze free liquid of an overbased alkaline earth metal salt of a fattyacid comprises reacting an alkaline earth metal base and a fatty acidwith an equivalent ratio of metal base to the fatty acid being greaterthan 1:1 in the presence of a mixture of liquid hydrocarbon. Asurfactant and catalyst promote the reaction. The mixture is acidifiedand preferably carbonated to produce amorphous alkaline earth metalcarbonate. During carbonation, a dispersion is added containing alkalineearth metal base, liquid hydrocarbon and an aliphatic alcohol having atleast 8 carbon atoms in relative amounts at a controlled rate of baseaddition to produce a stable haze free liquid reaction product. Water isremoved from the reaction product to produce a shelf stable haze freeliquid overbased alkaline earth metal salt. Generally, it is preferredthat the entire process be conducted in the absence of free oxygen and,for this purpose, an atmosphere of nitrogen is used.

[0024] As developed above, one of the important features of the methodis the step of adding during carbonation a dispersion of alkaline earthmetal base, liquid hydrocarbon and an aliphatic alcohol having at least8 carbon atoms at a controlled rate of base addition to produce thestable haze free liquid. It has been found that the addition of adispersion of the base in the liquid hydrocarbon and aliphatic alcoholprotects or passivates the base, thereby enabling the formation of astable haze free liquid reaction product. By protecting or passivatingthe base, carbonation proceeds to produce amorphous alkaline earth metalcarbonate. Unexpectedly, the reaction proceeds without the need toremove water during the reaction and results in a very stable haze freeliquid reaction product. At the end of the reaction, water is removed,preferably to the level of less than 1%, more preferably less than 0.3%or 0.1%, in the obtainment of the shelf stable liquid overbased salt.The removal of water which is added during the reaction or formed by thereaction is necessitated because it forms a separate phase which impedeseither the product of the reaction or the formation of a shelf stablehaze free liquid.

[0025] Other features of the method include filtering the product of thereaction to produce a shelf or thermodynamically stable liquid at aproduct filtration rate of at least about 300 ml per 10 minutes. In apreferred form of the invention, the product which is produced isfilterable to remove unwanted byproducts and enhance the shelf stabilityof the overbased liquid. For example, with a Buchner funnel having a 15cm diameter under vacuum of about 25-30 inches Hg with a Whatman No. 1filter and a diatomaceous filtering aid (Celite® 512-577), the productis filterable at satisfactory rates. One of the important discoveries ofthe method of this invention is the ability to filter the reactionproduct to form a stable haze free liquid at filtration rates whichheretofore were unachievable. This was especially the case when higherlevels of metal content in the overbased liquids were desired,especially overbased calcium liquids. Thus, filtration removesundesirable impurities including silica, iron oxide and other metalspecies, unreacted calcium hydroxide, calcium carbonate, and otheroxides which may contribute to lack of stability. These byproducts orimpurities may comprise up to about 6% of byproduct of the reaction.

[0026] Throughout this specification and claims, the term “basic” or“overbased” as applied to the alkaline earth metal salts is used torefer to metal compositions wherein the ratio of total metal containedtherein to the fatty acid moieties is greater than the stoichiometricratio of the neutral metal salt. That is, the number of metalequivalents is greater than the number of equivalents of the fatty acid.In some instances, the degree to which excess metal is found in thebasic metal salt is described in terms of a “metal ratio”. Metal ratioas used herein indicates the ratio of total alkaline earth metal in theoil-soluble composition to the number of equivalents of the fatty acidor organic moiety. The basic metal salts often have been referred to inthe art as “overbased” or “superbased” to indicate the presence of anexcess of the basic component.

[0027] The process of the present invention may be used to prepare shelfstable liquids of the alkaline earth metal carboxylates of the fattyacids. As stated above, the method may be practiced without the use ofphenol promoter or phenolic reaction product. Therefore, liquidoverbased barium fatty acid carboxylates have been made without the needfor a phenol or phenolic reaction product in order to achieve a shelfstable haze free liquid. In the case of liquid overbased calcium fattyacid carboxylates, shelf stable haze free products are obtained withouta phenol where the aliphatic alcohol having at least 8 carbon atoms isemployed.

[0028] The alkaline earth metal bases utilized as a reaction componentmay be derived from any alkaline earth metals and, of these, calcium andbarium bases are particularly preferred. The metal bases include metaloxides and hydroxides and, in some instances, the sulfides, hydrosulfides, etc. While a phenolic component or reactant may preferably beexcluded from a reaction, in the case of liquid overbased calciumproducts, the phenol or alkyl phenol may be included to yield liquidoverbased products. As stated above, the fatty acids, or mixturesthereof, as identified above may be used in the reaction mixture. Forexample, a surfactant that facilitates the reaction is the alkalineearth metal carboxylate of the fatty acid that is formed in situ. Othersurfactants may be included, for example, general purpose surface activeagents identified under the trademark Tween which are polyoxyethylenederivatives of fatty acid partial esters of sorbitol anhydrides,particularly mono- and di-oleates of the ethoxylated sorbitol, andpolyisobutyle succinic acid. Furthermore, it is desirable to include acatalyst to facilitate the speed of the reaction such as propionic acid,citric acid, acetic acid and adipic acid. The hydrocarbon liquidemployed in the process and the liquid reaction products generallyincludes any hydrocarbon diluent. Most generally, the liquid hydrocarbonis selected from the group of an oil, mineral spirits and non-aromatichydrocarbons.

C. Amounts of Reactants and Catalysts

[0029] The amount of alkaline earth metal base utilized in thepreparation of basic salts is an amount which is more than oneequivalent of the base per equivalent of fatty acid or organic moiety,and more generally, will be an amount sufficient to provide at leastthree equivalents of the metal base per equivalent of the acid. Largeramounts can be utilized to form more basic compounds, and the amount ofmetal base included may be any amount up to that amount which is nolonger effective to increase the proportion of metal in the product.When preparing the mixture, the amount of fatty acid and the alcoholincluded in the mixture is not critical except that the ratio ofequivalents of the metal base of the combination of the other componentsin the mixture should be greater than 1:1 in order to provide a basicproduct. More generally, the ratio of equivalents will be at least 3:1.In those instances where phenol may be present in making an overbasedcalcium, the ratio of equivalents of monocarboxylic acid to phenolshould be at least about 1.1:1; that is, the monocarboxylic acid ispresent in excess with respect to the phenol.

[0030] The ranges of hydrocarbon oil, aliphatic alcohol (preferablyisodecanol), butyl Carbitol and triethylene glycol have been selectedsuch that, in the presence of the alkaline earth fatty acid salt (i.e.Ca oleate) which acts as a primary surfactant, the mixture forms astable inverse microemulsion of the metal carbonate, water, andsurfactant (internal phase) and surfactant, cosurfactant, andhydrocarbon (external continuous phase).

[0031] The acceptable ratios of hydrocarbon oil to cosurfactantaliphatic alcohol (isodecanol) are about 2:1 to about 4:1, with about2:1 preferred. The glycol ethers may be used at about 1-15% of the finalproduct, butyl Carbitol preferably at about 6%, and triethylene glycolat about 0-2%, preferably at about 0.6%.

[0032] The lime slurry which is added to the oleic acid in the reactionis formulated to be an easily pumpable mixture with the generalcomposition of about 40-50% lime, about 25-40% hydrocarbon oil, about10-25% isodecanol, and about 0-10% butyl Carbitol. The butyl Carbitolamount that is needed to make a pumpable slurry increases as the % limein the slurry increases.

[0033] The reaction mixture for an overbased calcium oleate, afteraddition of the slurry and carbonation with carbon dioxide, preferablyhas the following composition ranges: Ca oleate (surfactant) about15-30% Ca carbonate about 9-35% Hydrocarbon oil about 30-35% Isodecanol(cosurfactant) about 15-18% Butyl Carbitol about 4-6% Triethyleneglycolabout 0-0.8%

[0034] The catalyst, propionic acid or a lower aliphatic mono, di, ortricarboxylic acid is used in the amount of about 0-0.1% of the finalreaction mixture.

[0035] Substitution of magnesium, strontium, or barium for calcium inthe overbased salt is done on an equivalent basis of the metalhydroxide. On the basis of the final reaction mixture, the followingamounts may be used: Ca(OH)₂ (lime) about 15-30% Mg(OH)₂ about 12-24%Sr(OH)₂ about 25-50% Ba(OH)₂ about 35-50%

[0036] The step of carbonation involves treating the mixtures describedabove with an acidic gas in the absence of free oxygen until thetitratable basicity is determined using phenolphthalein. Generally, thetitratable basicity is reduced to a base number below about 10. Themixing and carbonation steps of the present invention require no unusualoperating conditions other than preferably the exclusion of free oxygen.The base, fatty acid and liquid hydrocarbon are mixed, generally heated,and then treated with carbon dioxide as the acidic gas, and the mixturemay be heated to a temperature which is sufficient to drive off some ofthe water contained in the mixture. The treatment of the mixture withthe carbon dioxide preferably is conducted at elevated temperatures, andthe range of temperatures used for this step may be any temperatureabove ambient temperature up to about 200° C., and more preferably froma temperature of about 75° C. to about 200° C. Higher temperatures maybe used such as 250° C., but there is no apparent advantage in the useof such higher temperatures. Ordinarily, a temperature of about 80° C.to 150° C. is satisfactory.

[0037] By the term “acidic gas” as used in this specification and in theclaims is meant a gas which upon reaction with water will produce anacid. Thus, such gases as sulfur dioxide, sulfur trioxide, carbondioxide, carbon disulfide, hydrogen sulfide, etc., are exemplary of theacidic gases which are useful in the process of this invention. Of theseacids, sulfur dioxide and carbon dioxide are preferred, and the mostpreferred is carbon dioxide. When carbon dioxide is used the alkalineearth carbonate is formed. When the sulfur gases are used, the sulfate,sulfide and sulfite salts are formed.

D. Halogen-Containing Polymer

[0038] A halogen-containing polymer, such as a vinyl halide resin, mostcommonly stabilized with the basic metal salts of this invention ispolyvinyl chloride. It is to be understood, however, that this inventionis not limited to a particular vinyl halide resin such as polyvinylchloride or its copolymers. Other halogen-containing resins which areemployed and which illustrate the principles of this invention includechlorinated polyethylene, chlorosulfonated polyethylene, chlorinatedpolyvinyl chloride, and other vinyl halide resin types. Vinyl halideresin, as understood herein, and as appreciated in the art, is a commonterm and is adopted to define those resins or polymers usually derivedby polymerization or copolymerization of vinyl monomers including vinylchloride with or without other comonomers such as ethylene, propylene,vinyl acetate, vinyl ethers, vinylidene chloride, methacrylate,acrylates, styrene, etc. A simple case is the conversion of vinylchloride H₂C=CHCl to polyvinyl chloride (CH₂CHCl—)_(n) wherein thehalogen is bonded to the carbon atoms of the carbon chain of thepolymer. Other examples of such vinyl halide resins would includevinylidene chloride polymers, vinyl chloride-vinyl ester copolymers,vinyl chloride-vinyl ether copolymers, vinyl chloride-vinylidenecopolymers, vinyl chloride-propylene copolymers, chlorinatedpolyethylene, and the like. Of course, the vinyl halide commonly used inthe industry is the chloride, although others such as bromide andfluoride may be used. Examples of the latter polymers include polyvinylbromide, polyvinyl fluoride, and copolymers thereof.

[0039] Metal compound heat stabilizers of vinyl halide resincompositions are well known. These metal compounds serve to capture HClliberated during heat processing of the vinyl halide resin compositioninto its final shape. The metal can be lead, cadmium, barium, calcium,zinc, strontium, bismuth, tin, or antimony, for example. The stabilizersare usually metal salts of a carboxylic acid, advantageously of a C₈-C₂₄carbon chain link monocarboxylic acid such as lauric, oleic, stearic,octoic, or similar fatty acid salts. Metal salts of alkyl phenates maybe used. Mixed metal salts of such acids, and their preparation, arefamiliar to those skilled in the art to which this present inventionpertains. Mixed metallic carboxylates involving calcium/zinc orbarium/zinc blends alone and in combination with other stabilizers oradditives such as beta-diketones, phosphite salts and phenolicantioxidants have been used. The metal stabilizer is a mixed metal saltof a carboxylic acid. Mixed metal salts of such acids, and theirpreparation, are also familiar to those skilled in the art to which thispresent invention pertains.

E. End Uses for the Stabilzers

[0040] The liquid stabilizers or mixed metal stabilizers of thisinvention may be used in a number of end products. Examples include:wall covering, flooring (vinyl tile and inlay), medical devices, dipcoating, chair mat, banner film, pigment dispersion, vinyl siding,piping, fuel additive, cosmetic, ceiling tile, roofing film, wear layer,play balls or toys, teethers, fencing, corrugated wall panels,dashboards, and shifter boots.

[0041] The following Examples illustrate the preparation of the shelfstable haze free liquids of the overbased salts in accordance with themethod of the present invention, but these examples are not consideredto be limiting the scope of this invention. Unless otherwise indicatedin the following examples and elsewhere in the specification and claims,all parts and percentages are by weight, and all temperatures are indegrees fahrenheit.

EXAMPLE 1 10% Overbased Calcium Oleate/Carbonate

[0042] A phenol-free 10% overbased calcium oleate/carbonate was preparedaccording to this Example. A mixture of 308.42 g of oleic acid (1.100moles), 213.15 g mineral oil, 154.14 g of isodecyl alcohol, 63.08 g ofbutyl Carbitol, 8.70 g of triethylene glycol, 26.97 g of water and 0.87g of propionic acid was heated to 190° F., with stirring, under anitrogen atmosphere. To the stirred mixture there was continuously addeda dispersion comprised of 38.98 g mineral oil, 13.86 g isodecyl alcohol,3.71 g butyl Carbitol and 43.28 g of lime (0.5498 moles) for about 33minutes to produce a solution of calcium oleate in the mixture. Thedispersion was added at a rate of about 3 g per minute. At this point inthe reaction, the mixture tested basic with phenolphthalein (about 10-12pH). Then, to the stirred mixture there was continuously added, over aperiod of about 3 hours and 56 minutes, a dispersion comprised of 276.25g mineral oil, 98.23 g isodecyl alcohol, 26.31 g butyl Carbitol and306.75 g lime (3.897 moles) while the mixture was being treated withcarbon dioxide at 1.5 SCFH at 195-200° F. The dispersion was also addedat a rate of about 3 g per minute. The basicity of the reaction waschecked to maintain the basicity during the reaction. When the reactionmixture tested nearly neutral to phenolphthalein, the carbon dioxideaddition was discontinued. The reaction mixture was then heated to 300°F. and a total of 99.36 g of water was removed via a Dean-Stark trap.The resulting product mixture was stirred and 24.00 g of filter aid(diatomaceous earth) was added. The product mixture was filtered withsuction, as stated above in the description, at about 300 ml per 10minutes, yielding a clear, amber, mobile liquid filtrate of overbasedcalcium oleate/carbonate which remained clear upon cooling to roomtemperature. The filtrate was analyzed to contain 10.4% Calcium byweight.

EXAMPLE 2 14% Overbased Calcium Oleate/Carbonate

[0043] A phenol-free overbased calcium oleate/carbonate containing 14%calcium by weight was made according to this Example. In a 3-liter resinkettle equipped with an overhead stirrer, two gas inlet tubes, athermocouple, heating mantle and Dean-Stark trap with condenser, wasadded 1700 g of a 9.89% overbased calcium oleate/carboxylate made by themethod of the previous example and 42.5 g of deionized water. Themixture was heated with stirring under a nitrogen atmosphere to atemperature of 195° F., and a slurry containing 385 g of hydrated lime(94% calcium hydroxide), 231 g of hydrocarbon oil, 96.25 g of isodecylalcohol, and 57.75 g of butyl Carbitol was added at a rate of 3.42 g perminute over a 3 hour 45 minute period. After 5 minutes of slurryaddition, carbon dioxide was added to the reaction at a rate of 1.2standard cubic feet per hour. During the carbonation, a temperature of195-200° F. was maintained and pH was monitored as in Example 1.

[0044] After the slurry addition was finished, the carbon dioxideaddition was continued until the reaction mixture was neutral, as shownby a colorless sample when tested with phenolphthalein. The reactionmixture was then heated to 300° F. and both the water added and thewater produced in the reaction was removed via the Dean-Stark trap. Tothe dehydrated reaction product was added 75 g of diatomaceous earth andthe product was filtered with suction, as above in Example 1, yielding aclear, amber, mobile liquid filtrate of overbased calciumoleate/carboxylate which remained clear on cooling to room temperature.The filtrate was analyzed to contain 14.5% calcium by weight.

Shelf Stable Haze Free Liquid Tests

[0045] Shelf Stability of the Phenol-Free Liquid Overbased CalciumCarboxylate/Carbonate of Example 1

[0046] Shelf stability of the phenol-free liquid overbased calciumcarboxylate/carbonate of Example 1 (referred to hereinafter as NewCalcium) was measured using a turbidity meter over a period of 60 daysin order to study its shelf stability properties. The Old Calciumreferred to hereinafter is a formerly commercially available overbasedcalcium carboxylate containing 14% Ca (Lubrizol's product LZ 2118, OMGPlastistab 2118).

[0047] The following Table I summarizes the results: TABLE I 1 Day 7Days 10 Days 22 Days 60 Days Stabilizer containing 7.8 7.7 8.0 7.7 7.5New Calcium Stabilizer containing >200 >200 >200 >200 >200 Old Calcium

[0048] Turbidity readings were measured in Jackson Turbidity Units(JTU). The turbidity observation between 1-30 indicates that the productis free from haze, and the observation above 30 to 200 JTU indicatesthat the product is hazy in nature. If the turbidity observation staysconstant over a period of time, this means that the product possessesgood shelf stability. This means that the product does not pick up anyhaze or undergo change in physical appearance over a period of time.

[0049] The data of Table I shows that the New Calcium possessed goodshelf stability over a 60-day period, whereas the commercially availableOld Calcium is hazy in nature.

[0050] Shelf Stability of Mixed Metal Stabilizer of Phenol-FreeOverbased Calcium Carboxvlate/Carbonate and Zinc Carboxylate(Calcium/Zinc Stabilizer)

[0051] Shelf stability of mixed metal calcium/zinc stabilizerscontaining New Calcium (Example 1) and Old Calcium was also monitoredover a period of 24 days as shown in Table II. The stabilizerformulation contained 5% Ca, 1.2% Zn (zinc octoate), 3.5% P (diphenylisodecyl phosphite), 5% carboxylic acid (oleic acid),3% anti-oxidant, 3%β-diketone (dibenzoyl methane) and diluent. TABLE II 1 Day 4 Days 7 Days10 Days 24 Days Stabilizer containing 23.2 25.1 26.2 24.4 24.7 NewCalcium Stabilizer containing >200 >200 >200 >200 >200 Old Calcium

[0052] The data illustrates that incorporation of New Calcium, versusOld Calcium, makes the mixed metal stabilizer shelf stable and hazefree.

[0053] The above shelf stability tests were repeated by incorporatingthe New Calcium into a second stabilizer formulation. Shelf stabilityand clarity of a calcium/zinc stabilizer containing New and Old Calciumwas monitored over a 24-day period, and the results are shown in TableIII. Stabilizer formulation contained 5% Ca, 1.2% Zn (zinc octoate),3.4% P (diphenyl decyl phosphite) 6% carboxylic acid (3% oleic acid/3%benzoic acid), 3% nonyl phenol as an anti-oxidant, 2% β-diketone (octylbenzoyl methane) and diluent. TABLE III 1 Day 4 Days 7 Days 10 Days 24Days Stabilizer containing 25.1 26.3 28.1 26.5 26.8 New CalciumStabilizer containing >200 >200 >200 >200 >200 Old Calcium

[0054] Again, the data illustrates that the New Calcium produces a shelfstable haze free mixed metal stabilizer versus the Old Calcium.

[0055] Shelf Stability of Mixed Metal Stabilizer of OverbasedCalcium/Tin Carboxylate Stabilizers (Calcium/Tin Stabilizer)

[0056] Shelf stability of a calcium/tin stabilizer containing NewCalcium (Example 1) and Old Calcium was monitored over a period of 25days as shown in Table IV. Stabilizer formulation contained 5% Ca, 1.5%Sn (tin maleate), 3% P (diphenyl decyl phosphite), 5% carboxylic acid(oleic acid), 2% anti-oxidant (bisphenol-A), 3% β-diketone (dibenzoylmethane) and diluent. TABLE IV 1 Day 4 Days 7 Days 11 Days 25 DaysStabilizer containing 52 54 58 61 62 New Calcium Stabilizercontaining >200 >200 >200 >200 >200 Old Calcium

[0057] The data illustrates that the incorporation of New Calcium,versus Old Calcium, makes the stabilizer shelf stable.

[0058] Performance Comparisons: Thermal Degradation of PVC

[0059] The New Calcium (Example 1) and Old Calcium were incorporatedinto mixed metal stabilizer compositions for the purpose of observingtheir relative rate of thermal degradation in PVC. The stabilizercompositions are as follows: Stabilizer formulation A B New Calcium 5.5%Ca — Old Calcium (2118) — 5.5% Ca Zinc carboxylate 1.2% Zn 1.2% ZnOrganic Phosphite 3.0% P 3.0% P Carboxylic Acid 4.0% 4.0% Anti-oxidant3.0% 3.0% Beta Diketone 3.0% 3.0% Diluent as needed as needed

[0060] The performances of these stabilizers A and B were observed in aPVC formulation containing 100 parts of PVC resin (K value 66), 30 partsphthalate plasticizer, 3 parts of epoxidized soybean oil and 2 parts ofeither stabilizer A or B.

[0061] Stabilized PVC compounds were then milled at 350-360° F. for 5minutes at 25 mil thickness. The thermal stability was carried out at375° F. over 56 minutes. Yellowness [+b chromaticity of CIELAB colorspace (Commission Internationale de l'Eclairage) developed in 1976] wasmeasured with a Minolta calorimeter. The yellowness values of the rateof thermal degradation are shown in the following Table V.

[0062] The PVC formulation containing the stabilizer with the NewCalcium (A) develops color at a slower rate than the PVC formulationusing the stabilizer with the Old Calcium (B). TABLE V Time (minutes)New Calcium A Old Calcium B 7 9.68 10.11 14 10.52 10.68 21 11.76 11.5428 15.25 14.89 35 18.39 19.59 42 38.57 47.77 49 46.69 56.92 56 60.1169.33

[0063] Performance Comparisons: Clarity

[0064] The New Calcium (Example 1) and Old Calcium, along with a calciumcarboxylate (C₈), were incorporated into mixed metal stabilizercompositions for the purpose of observing their influence on the clarityof the PVC application. The stabilizer compositions are as follows:Stabilizer Formulation A B C New Calcium 5.5% — — Old Calcium — 5.5% —Calcium Carboxylate (C₈) — — 5.5% Ca Zinc carboxylate 1.2% Zn 1.2% Zn1.2% Zn Organic Phosphite 3.4% P 3.4% P 3.4% P Carboxylic Acid 5.0% 5.0%5.0% Anti-oxidant 3.0% 3.0% 3.0% Beta Diketone 2.0% 2.0% 2.0% Diluent asneeded as needed as needed

[0065] The relative degree of clarity of the 0.25 inch pressed PVCformulations containing either stabilizer A, B or C was observed after 5minutes of exposure to 350° F. and 15,000 pounds pressure. The PVCformulation comprised of 100 parts PVC resin (K value 66), 30 partsphthalate plasticizer, 3 parts of epoxidized soybean oil and 2 parts ofeither stabilizer A, B or C.

[0066] The pressed PVC samples were placed vertically near printedmaterial to determine the crispness of the print when looking throughthe press. Stabilizer A and B gave comparable crispness. However, bothstabilizer A and B gave better clarity or crispness than stabilizer C.

[0067] Performance Comparisons: Plate Out

[0068] The New Calcium (Example 1) and Old Calcium along with anon-carbonated calcium carboxylate were incorporated into mixed metalstabilizer compositions for the purpose of observing their influence onthe resistance to plate out of the stabilizer during processing of thevinyl formulation. The stabilizer compositions have been identifiedabove as A, B and C with A containing the New Calcium, B containing theOld Calcium and C containing the non-carbonated calcium carboxylate.

[0069] Plate out is determined by introducing a red pigment into a PVCformulation containing the stabilizer and allowing the pigment tomigrate from the formulation to the metal rolls of a two roll mill at340° F. A white clean up compound is then placed onto the rolls and thedegree of plate out is determined by the amount of red picked up by theclean up compound. The colorimeter assigns a numerical value on theCIElab scale for the degree of redness or plate out (+a). Red pigmentedformulation: Clean up compound 100 PVC resin 100 PVC resin 40 phthalateplasticizer 40 phthalate plasticizer 8 epoxidized soybean oil 8epoxidized soybean oil 0.2 Stearic acid 0.2 Stearic acid 2 red 2Bpigment 4 Titanium dioxide 1.5 stabilizer 3 lead phosphite

[0070] The red formulation is milled for 4 minutes undisturbed afterwhich the clean up compound is introduced and milled for three minutesundisturbed.

[0071] Colorimeter readings, +a value indicating increasing degree ofred: Sample a-value A −2.28 B −2.07 C +24.3

[0072] There is essentially no difference between the New and OldCalcium as far as plate out resistance. However, there is a significantdifference between A and C where the New Calcium provides superior plateout resistance.

[0073] The above description provides a disclosure of particularembodiments of the invention and is not intended for the purpose oflimiting the same thereto. As such, the invention is not limited to onlythe above described embodiments, rather, it is recognized that oneskilled in the art would understand alternative embodiments in view ofthe above description that fall within the scope of the invention.

What is claimed is:
 1. A shelf stable haze free liquid of an overbasedalkaline earth metal salt of a fatty acid comprising an alkaline earthmetal salt from the group consisting of carbonate, sulfate, sulfide andsulfite, an alkaline earth metal carboxylate of a fatty acid, a liquidhydrocarbon, and an aliphatic alcohol having at least 8 carbon atoms,said liquid being essentially free of a phenol or phenolic derivative.2. The shelf stable haze free liquid of claim 1 wherein said fatty acidis a C₁₂-C₂₂ fatty acid.
 3. The shelf stable haze free liquid of claim 1wherein said fatty acid is oleic acid.
 4. The shelf stable haze freeliquid of claim 1 wherein said alkaline earth metal is selected from thegroup consisting of calcium, barium, magnesium and strontium.
 5. Theshelf stable haze free liquid of claim 1 wherein said alkaline earthmetal is calcium.
 6. The shelf stable haze free liquid of claim 1wherein the overbased alkaline earth salt is calcium oleate/carbonate.7. The shelf stable haze free liquid of claim 1 which is a microemulsionhaving micells of the alkaline earth metal carbonate and an alkalineearth metal carboxylate of a fatty acid, and a continuous phase of theliquid hydrocarbon and the aliphatic alcohol.
 8. The shelf stable hazefree liquid of claim 1 wherein the alcohol has 8 to 14 carbon atoms. 9.The shelf stable haze free liquid of claim 1 wherein said alcohol isselected from the group of isodecanol, dodecanol, octanol, tridecanoland tetradecanol, and mixtures thereof.
 10. The shelf stable haze freeliquid of claim 9 which further contains a glycol or a glycol ether. 11.The shelf stable haze free liquid of claim 10 wherein the glycol orglycol ether is selected from the group consisting of diethylene glycolmonobutyl ether, triethylene glycol, dipropylene glycol, diethyleneglycol monomethyl ether, ethylene glycol monobutyl ether, and mixturesthereof.
 12. The shelf stable haze free liquid of claim 1 containingabout 4% up to about 36% by weight of alkaline earth metal.
 13. Theshelf stable haze free liquid of claim 12 wherein the alkaline earthmetal is calcium which is contained in an amount of about 9% to about15% by weight.
 14. A shelf stable haze free liquid of an overbasedcalcium salt of a fatty acid comprising calcium carbonate, calciumcarboxylate of a fatty acid, a liquid hydrocarbon, and an aliphaticalcohol having at least 8 carbon atoms.
 15. The shelf stable haze freeliquid of claim 14 which is essentially free of a phenol or phenolicderivative.
 16. The shelf stable haze free liquid of claim 14 whereinthe liquid hydrocarbon is an oil.
 17. The shelf stable haze free liquidof claim 14 wherein the liquid hydrocarbon is selected from the groupconsisting of an oil, mineral spirits and non-aromatic hydrocarbons. 18.The shelf stable haze free liquid of claim 14 wherein said fatty acid isa C₁₂-C₂₂ fatty acid.
 19. The shelf stable haze free liquid of claim 14wherein said fatty acid is oleic acid.
 20. The shelf stable haze freeliquid of claim 14 which is a microemulsion having micells of thealkaline earth metal carbonate, and an alkaline earth metal carboxylateof a fatty acid, and a continuous phase of the liquid hydrocarbon andthe aliphatic alcohol.
 21. The shelf stable haze free liquid of claim 14wherein said alcohol is isodecanol.
 22. The shelf stable haze freeliquid of claim 20 wherein the continuous phase further contains aglycol or a glycol ether.
 23. The shelf stable haze free liquid of claim22 wherein the glycol or glycol ether is selected from the groupconsisting of diethylene glycol monobutyl ether, triethylene glycol,dipropylene glycol, diethylene glycol monomethyl ether, ethylene glycolmonobutyl ether, and mixtures thereof.
 24. The shelf stable haze freeliquid of claim 14 containing about 4% up to about 36% by weightcalcium.
 25. The shelf stable shelf stable haze free liquid of claim 14wherein calcium is contained in an amount of at least about 9% to about15% by weight.
 26. A process for preparing a shelf stable haze freeliquid of an overbased alkaline earth metal salt of a fatty acidcomprising reacting an alkaline earth metal base and a fatty acid withan equivalent ratio of metal base to fatty acid being greater than 1:1in the presence of liquid hydrocarbon, carbonating the mixture toproduce amorphous alkaline earth metal carbonate, adding duringcarbonation a dispersion of alkaline earth metal base, a liquidhydrocarbon and an aliphatic alcohol having at least 8 carbon atoms inrelative amounts at a controlled rate of alkaline earth metal baseaddition to produce a stable haze free liquid reaction product, andremoving water from the reaction product to obtain a shelf stable hazefree liquid overbased alkaline earth metal salt.
 27. The process ofclaim 26 further comprising filtering the liquid reaction product toproduce a thermodynamically stable liquid at a product filtration rateof at least about 300 ml per 10 minutes.
 28. The process of claim 26wherein said fatty acid is a C₁₂-C₂₂ fatty acid.
 29. The process ofclaim 26 wherein said fatty acid is oleic acid.
 30. The process of claim26 wherein water is removed to provide a microemulsion product havingless than about 1% by weight water of the total product.
 31. The processof claim 26 wherein said alkaline earth metal is selected from the groupconsisting of calcium, barium, magnesium and strontium.
 32. The processof claim 26 wherein said alkaline earth metal is calcium.
 33. Theprocess of claim 26 wherein the overbased salt is calciumoleate/carbonate.
 34. The process of claim 26 to produce the overbasedsalt which is essentially free of a phenol or phenolic derivative. 35.The process of claim 26 wherein said aliphatic alcohol has 8 to 14carbon atoms.
 36. The process of claim 35 wherein the alcohol isisodecanol.
 37. The process of claim 36 wherein the continuous phasefurther contains a glycol or a glycol ether.
 38. The process of claim 37wherein the glycol or glycol ether is selected from the group consistingof diethylene glycol monobutyl ether, triethylene glycol, dipropyleneglycol, diethylene glycol monomethyl ether, ethylene glycol monobutylether, and mixtures thereof.
 39. The process of claim 26 by reacting onthe basis of the final reaction mixture an amount of an alkaline earthmetal base selected from the group consisting of about 15-30% calciumhydroxide, about 12-24% magnesium hydroxide, about 25-50% strontiumhydroxide, and about 35-50% barium hydroxide, and mixtures thereof. 40.The process of claim 39 wherein the alkaline earth metal base is calciumhydroxide and the fatty acid is oleic acid.
 41. The process forpreparing a shelf stable haze free liquid of an overbased calciumoleate/carbonate comprising reacting calcium hydroxide base and oleicacid with an equivalent ratio of the base to the acid being greater than1:1 in the presence of a mixture of liquid hydrocarbon and catalyst,carbonating the mixture to produce amorphous calcium carbonate, addingduring carbonation a dispersion of calcium hydroxide, liquid hydrocarbonand cosurfactant aliphatic alcohol having at least 8 carbon atoms inrelative amounts at a controlled rate of calcium hydroxide addition toproduce a stable haze free liquid reaction product, and removing waterfrom the reaction product to provide a shelf stable haze free overbasedcalcium oleate/carbonate.
 42. The process of claim 41 comprising thefurther step of filtering the liquid reaction product to removebyproducts or impurities.
 43. The process of claim 41 which is conductedessentially free of a phenol or a phenolic derivative.
 44. The processof claim 41 wherein the catalyst is selected from the group consistingof propionic acid, citric acid, acetic acid and adipic acid.
 45. Theprocess of claim 41 wherein the surfactant is calcium oleate borne bythe reaction of the base and the oleic acid in situ.
 46. The process ofclaim 41 wherein the cosurfactant is an aliphatic alcohol having 8 to 14carbon atoms.
 47. The process of claim 46 wherein the alcohol selectedis isodecanol in the presence of diethylene glycol monobutyl ether andtriethylene glycol.
 48. The process of claim 46 wherein the haze freeliquid calcium oleate is a microemulsion having amorphous calciumcarbonate within the micelles of the microemulsion.
 49. The process ofclaim 41 wherein after the addition of the dispersion and carbonationwith carbon dioxide the mixture contains about 15-30% calcium oleate,about 9-35% calcium carbonate, about 30-35% hydrocarbon oil, about15-18% idodecanol, and about 4-6% glycol or glycol ether.
 50. Theprocess of claim 49 wherein the dispersion contains about 40-50% calciumhydroxide, about 25-40% hydrocarbon oil, about 10-25% isodecanol andabout 0-10% glycol or glycol ether.
 51. A halogen-containing polymercomposition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 1. 52. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 2. 53. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 3. 54. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 4. 55. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 5. 56. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 6. 57. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 8. 58. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 10. 59. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 11. 60. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 12. 61. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 13. 62. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 15. 63. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 16. 64. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 17. 65. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 18. 66. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 24. 67. A halogen-containingpolymer composition comprising a halogen-containing polymer and a heatstabilizing amount of the liquid of claim
 25. 68. A mixed metalstabilizer composition for a halogen-containing polymer comprising ametal compound stabilizer selected from the group consisting ofcompounds of antimony, barium, calcium, cadmium, zinc, lead, strontium,bismuth and tin, and mixtures thereof, and a shelf stable haze freeliquid of claim 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 12, 13, 15, 16, 17, 18,24, and 25, said metal compound stabilizer and liquid in relativeamounts for stabilizing said polymers.
 69. A mixed metal stabilizercomposition for a halogen-containing polymer comprising a metal compoundstabilizer and a shelf stable haze free liquid of calciumoleate/carbonate, said stabilizer and liquid in relative amounts forstabilizing said polymer.